CN102459116B - Expansive admixture and method for producing same - Google Patents

Expansive admixture and method for producing same Download PDF

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Publication number
CN102459116B
CN102459116B CN201080025544.3A CN201080025544A CN102459116B CN 102459116 B CN102459116 B CN 102459116B CN 201080025544 A CN201080025544 A CN 201080025544A CN 102459116 B CN102459116 B CN 102459116B
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expanding material
calcium carbonate
carbon dioxide
grog
cement
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CN102459116A (en
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樋口隆行
森泰一郎
石田秀朗
吉野亮悦
盛冈实
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • C04B7/527—Grinding ; After-treatment of ground cement obtaining cements characterised by fineness, e.g. by multi-modal particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/48—Clinker treatment
    • C04B7/52—Grinding ; After-treatment of ground cement
    • C04B7/522—After-treatment of ground cement
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/18—Carbon capture and storage [CCS]

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

Disclosed is an expansive admixture having excellent storage stability, which is capable of making concrete expand greatly at an age of 2-7 days after placement of the concrete, while making the concrete has a high initial compressive strength. Also disclosed is a method for producing the expansive admixture. Specifically disclosed are: an expansive admixture which is characterized by being obtained by heating clinker or ground clinker, which contains quicklime, a hydraulic compound and anhydrous gypsum, in a carbon dioxide gas atmosphere, thereby producing calcium carbonate; and a method for producing the expansive admixture. It is preferable for the expansive admixture to contain particles in each of which all the quicklime, hydraulic compound, anhydrous gypsum and calcium carbonate are present. It is also preferable that the expansive admixture has a calcium carbonate content of 0.5-10% by mass and a Blaine specific surface area of 1,500-9,000 cm2/g. A cement composition is obtained by blending the expansive admixture into cement. During the production of the expansive admixture, it is preferable to produce calcium carbonate at a carbon dioxide gas flow rate of 0.01-0.1 L/min and at a temperature of 200-800 DEG C.

Description

Expanding material and manufacture method thereof
Technical field
The present invention relates to the reinforcement of concrete expanding material and the manufacture method thereof that in civil construction field, use.
Background technology
Someone has proposed just to have the surface of concrete expansion material (patent documentation 1), unslaked lime of excellent expansion characteristics under few addition by the expanding material for cement of calcium carbonate coating (patent documentation 2).In addition, the crushing material that someone proposes to make the surface carbon acidifying of light-burned unslaked lime to be used as cement concrete hardenite uses (patent documentation 3).
In the field of iron and steel, the object for inhibition as the moisture absorption of the lime of sweetening material, someone has proposed to make the technology (non-patent literature 1) of lime carbonation.
Prior art document
Patent documentation
Patent documentation 1: No. 4244261 communiques of Japanese Patent
Patent documentation 2: Japanese kokai publication sho 54-93020 communique
Patent documentation 3: Japanese kokai publication sho 58-154779 communique
Non-patent literature
Non-patent literature 1: the moisture absorption of part charcoal acidifying To I Ru unslaked lime suppress To つ い て, iron と Steel (about the moisture absorption that suppresses unslaked lime by part carbonating, iron and steel), 1978, Vol.64, No.2,56～65 pages
Summary of the invention
The problem that invention will solve
Expanding material in the past has following characteristic: by expanding significantly in after concrete placement 1 to 2, be gently expanded to thereafter material age 7 days.But, because the hydration reaction of the cement in concrete in material age 1～2 is not fully carried out, therefore having that matrix (matrix) is thick and creep is large, the prestress of reinforcing bar being introduced by expanding material becomes the situation about disappearing of being easy to.Thus, require to develop with few addition and the material age swell increment of 1～2 is few and can be material age 2～7, further gave significantly the expanding material of expansion on 5 to 7.Have in addition following problem: expanding material is in the past under the environment of high temperature and humidity Long-term Storage, and expansion character reduces, particularly in advance with cement mixing in the situation that, the reduction of expansion character becomes significantly.Expanding material is mixed in to cement and makes in advance expansive cement, there is following etc. advantage: not only can save the time of dropping in fresh concrete equipment, and can avoid because of cause expanding material to condense outstanding (pop out) phenomenon producing because of mixing deficiency.But, owing to existing problem as described above therefore cannot realize.
Therefore, problem of the present invention is to provide a kind of expanding material and manufacture method thereof, described expanding material can the material age after concrete placement be given concrete with large expansion in 2～7, makes concrete initial compressive strength high, and storage stability excellence.
For the scheme of dealing with problems
The present invention is: (1) a kind of expanding material, it is characterized in that, under carbon dioxide atmosphere by the grog that contains free lime, hydraulicity compound and dehydrated gyp-(clinker) thereby or chamotte powder mince heat treated and generate calcium carbonate obtain; (2) expanding material of (1), it contains the particle that has free lime, hydraulicity compound, dehydrated gyp-and calcium carbonate in same particle; (3) expanding material of (1) or (2), wherein the content of calcium carbonate is 0.5～10 quality %; (4) expanding material of any one in (1)～(3), wherein Brian specific surface area is 1500～9000cm 2/ g; (5) expanding material of any one in (1)～(4), wherein to aforementioned grog or chamotte powder being minced to heat treated generate calcium carbonate and in the material that obtains, further add dehydrated gyp-and obtain under carbon dioxide atmosphere; (6) expanding material of any one in (1)～(5), wherein to aforementioned grog or chamotte powder being minced to heat treated generate calcium carbonate and in the material that obtains under carbon dioxide atmosphere, further adds economization agent and obtains; (7) cement composition wherein coordinates the expanding material of any one in (1)～(6) to form in cement; (8) manufacture method of the expanding material of any one in (1)～(6), the heat treated that wherein under carbon dioxide atmosphere, the grog that contains free lime, hydraulicity compound and dehydrated gyp-or chamotte powder minced, generates calcium carbonate; (9) manufacture method of the expanding material of (8), wherein in carbonating processing vessel, filling grog or chamotte powder minces, is that temperature in 0.01～0.1L/min, container is to generate calcium carbonate under the condition of 200～800 DEG C at the carbon dioxide flow of every 1L volume of aforementioned container.
Invention effect
According to the present invention, can reach following effect: can obtain a kind of expanding material, described expanding material can the material age after concrete placement be given concrete with large expansion in 2～7, and the concrete material age compressive strength of 7 days is high, even if the reduction of Long-term Storage, expansion character is also few.
Embodiment
Be explained, part of using in the present invention, % are as long as referring to quality criteria without special stipulation.
In addition, the concrete of saying in the present invention is the general name to grout (cement paste), sand-cement slurry (cement mortar), cement concrete.
Expanding material of the present invention be with carbonic acid gas to grog or the chamotte powder material of processing and obtain that minces, described grog or chamotte powder mince by suitable mixed C aO raw material, Al 2o 3raw material, Fe 2o 3raw material, SiO 2raw material and CaSO 4raw material is also heat-treated and obtains.
The free lime of saying in the present invention refers to the material of so-called f-CaO.
The hydraulicity compound of saying in the present invention refers to by 3CaO3Al 2o 3caSO 4the hauyne (hauyne) representing, by 3CaOSiO 2(brief note is C 3s), 2CaOSiO 2(brief note is C 2s) Calucium Silicate powder representing, by 4CaOAl 2o 3fe 2o 3(brief note is C 4aF), 6CaO2Al 2o 3fe 2o 3(brief note is C 6a 2f), 6CaOAl 2o 3fe 2o 3(brief note is C 6aF) calcium aluminoferrite representing, 2CaOFe 2o 3(brief note is C 2the calcium ferrite etc. such as F), preferably comprises among them a kind or two or more.In expanding material of the present invention, the form of contained calcium carbonate is not particularly limited.
List Wingdale, slaked lime as CaO raw material; As Al 2o 3raw material lists bauxitic clay, aluminium slag etc.; As Fe 2o 3raw material is enumerated copper slag, commercially available ferric oxide, as SiO 2raw material lists silica etc., as CaSO 4raw material lists dihydrate gypsum, semi-hydrated gypsum and dehydrated gyp-.
Although have the situation that comprises impurity in these raw materials, do not become special problem in the scope that does not hinder effect of the present invention.As impurity, list MgO, TiO 2, ZrO 2, MnO, P 2o 5, Na 2o, K 2o, Li 2o, sulphur, fluorine, chlorine etc.
The heat treating method of the grog using in expanding material of the present invention is not particularly limited, and preferably uses electric furnace, kiln (kiln) etc. to burn till at the temperature of 1100～1600 DEG C, more preferably 1200～1500 DEG C.When 1100 DEG C of less thaies, expansion character is insufficient, has the situation that dehydrated gyp-decomposes in the time exceeding 1600 DEG C.
In the grog using in expanding material of the present invention, the ratio of contained each mineral is preferably following scope.The content of free lime is preferably 10～70 parts, more preferably 40～60 parts in 100 parts, grog.The content of hydraulicity compound is preferably 10～50 parts, more preferably 20～30 parts in 100 parts, grog.The content of dehydrated gyp-is preferably 1～50 part, more preferably 20～30 parts in 100 parts, grog.In addition, in the poor situation of the dehydrated gyp-in grog, preferably in addition add dehydrated gyp-and make expanding material.Outside aforementioned range, have following situation: swell increment is extreme becomes large and compressive strength reduces, or the material age swell increment of 2 to 7, the material age swell increment of 5 to 7 diminish.
The content of mineral can be confirmed by the past general analytical procedure.For example, can be by chippy sample is put into powder x-ray diffraction device, confirm generate mineral and utilize Rietveld method by data parsing, mineral are carried out quantitatively.In addition, qualification result that also can be based on chemical composition and powder x-ray diffraction, obtains mineral quantity by calculating.
Treatment condition for the preparation of the carbonic acid gas of expanding material of the present invention are preferably following scope.
The flow that flows to the carbonic acid gas of carbonating processing vessel is preferably 0.01～0.1L/min with respect to every 1L volume of carbonating processing vessel.When not enough 0.01L/min, have time-consuming situation in the carbonating of grog, even improve and also cannot obtain the further raising of carbonating processing speed again while exceeding 0.1L/min, this is uneconomic.Be explained, this condition is the condition that uses crucible to be statically placed in electric furnace, carbonic acid gas is flowed in the situation of reacting as carbonating processing vessel, by crucible, in the situation that grog and carbonic acid gas is reacted by other method, not limit by this.In addition, using the waste gas of discharging from lime firing furnace to substitute carbonic acid gas and carry out carbonating, is being preferred aspect raising expansion characteristics.
The temperature of carbonating processing vessel is preferably made as 200～800 DEG C.When 200 DEG C of less thaies, have the situation that the carbonation reaction of grog does not carry out, be once varied to calcium carbonate decarburization acidification reaction also occurs again even have in the time exceeding 800 DEG C, cannot generate the situation of calcium carbonate.
Be explained, the carbonating of grog can be directly by the grog carbonating of not pulverizing, carbonating after also grog can being pulverized.The carbonating processing vessel of saying in the present invention is not particularly limited, and can make grog contact with carbonic acid gas and react, and can be electric furnace, can be also fluidisation laminar process furnace, can be also the grinding machine that grog is pulverized.
About the ratio of calcium carbonate, in 100 parts, grog, be preferably 0.5～10 part, more preferably 1～5 part.The proportion of composing of each mineral has not in aforementioned range time cannot obtain excellent expansion character, initial compressive strength, the situation of storage stability.
The content of calcium carbonate can, by differential thermobalance (TG-DTA), the hot calorimetric measurement of differential (DSC) etc., come quantitatively according to the changes in weight of the decarbonate of following calcium carbonate.
Expanding material of the present invention preferably contains the particle that has free lime, hydraulicity compound, dehydrated gyp-and calcium carbonate in same particle.
Whether free lime, hydraulicity compound, dehydrated gyp-and calcium carbonate are present in same particle, can confirm by electron microscope etc.Particularly, can by with resin by expanding material embedding, carry out surface treatment with ar-ion beam, observe the structure of particle section, and confirm by carrying out ultimate analysis whether calcium carbonate is present in same particle.
The fines content of expanding material of the present invention is preferably 1500～9000cm in Brian specific surface area 2/ g, more preferably 2000～4000cm 2/ g.Not enough 1500cm 2when/g, have in situation about expanding for a long time and concrete structure is destroyed, when exceeding 9000cm 2when/g, have the situation that expansion character reduces.
The consumption of expanding material of the present invention changes because of concrete formula, thereby is not particularly limited, and conventionally in 100 parts of cement compositions that comprises cement and expanding material, is preferably 3～12 parts, more preferably 5～9 parts.When 3 parts of less thaies, have the situation that cannot obtain sufficient expansion character, when exceeding 12 parts and have the situation that becomes overplumping and expand crackle in concrete while using.
As the cement using in cement composition of the present invention, list: common, various portland cements (Portland cement) such as strong, super early strong, low-heat and middle heat early, the various mixed cements that mix blast furnace slag, flyash (fly ash), silicon-dioxide and obtain in these cement, and mixed filler cement of limestone powder etc.
Expanding material of the present invention can with sand, sandstone, water reducer, high-performance water reducing agent, AE water reducer, high performance AF dehumidifying agent, flowing agent, defoamer, thickening material, rust-preventive agent, frostproofer, economization agent, macromolecule emulsion, and the adjusting agent of condensing, and the fast hard material of cement, the clay minerals such as wilkinite, zeolite plasma permutoid, siliceous micropowder, calcium carbonate, calcium hydroxide, gypsum, Calucium Silicate powder, vinylon fiber, acrylic fibre, the fibrous materials such as carbon fiber etc. share.Particularly, by making expanding material of the present invention and economization agent combination, can give concrete with larger swell increment.The kind of economization agent is unrestricted, the particularly preferably alkylene oxide adducts of low molecular weight epoxy alkane copolymerization system, glycol ethers aminoalcohol derivative, lower alcohol, in commercially available product, list electrochemical industry system " エ ス ケ mono-ガ mono-De ", FPK Co., Ltd. system " Hibiguard ", Zhu Ben grease company system " Hibidan " and Taiheiyo Cement Corporation system " Tetraguard " etc.
Describe in detail by the following examples.
Embodiment
(experimental example 1)
By CaO raw material, Al 2o 3raw material, Fe 2o 3raw material, SiO 2raw material, CaSO 4raw material coordinates according to the mode that becomes the mineral ratio shown in table 1, after co-grinding, heat-treats and synthetic grog at 1350 DEG C, uses ball mill to be ground into Brian specific surface area for 3000cm 2/ g.This crushed material 25g is put into oxidation aluminum crucible and is placed in electric furnace, be that 0.05L/min, firing temperature are that the mode of 600 DEG C is reacted 1hr according to the flow of carbonic acid gas with respect to every 1L electric furnace internal volume, thereby the growing amount of generated calcium carbonate is carried out quantitatively having made expanding material.
Use this expanding material, in 100 parts of cement compositions that comprises cement and expanding material, use the expanding material of 4 parts or 7 parts, the indoor sand-cement slurry of preparing water/cement composition ratio=50%, cement composition/sand ratio=1/3 of 20 DEG C, thereby carry out the mensuration of tensile strain rate and compressive strength.
Be explained, as a comparison, also carried out same experiment for following material: the grog of not moisture hard material, dehydrated gyp-is pulverized to the material obtaining or they are carried out to carbon dioxide treatment and the expanding material that obtains (experiment No.1-8,1-9,1-10,1-11); Do not carry out carbon dioxide treatment and only grog is pulverized to the expanding material (experiment No.1-12,1-13,1-14) obtaining; Mixed carbonic acid calcium powder in not carrying out carbon dioxide treatment and only grog being pulverized to the expanding material obtaining and the expanding material that obtains (experiment No.1-15).In addition, implemented promotion storage test for each expanding material and expansive cement composition.
< uses material >
CaO raw material: Wingdale
Al 2o 3raw material: bauxitic clay
Fe 2o 3raw material: ferric oxide
SiO 2raw material: silica
CaSO 4raw material: dihydrate gypsum
Carbonic acid gas: commercially available product
Sand: JIS standard sand
Cement: normal portland cement, commercially available product
Calcium carbonate powders: commercially available product, 200 order product
< test method >
Mineral composition: obtain thereby the qualification result based on chemical constitution and powder x-ray diffraction calculates.
The growing amount of calcium carbonate: come quantitatively according to the changes in weight of the generations that decarbonate is followed of 500～750 DEG C of differential thermobalance (TG-DTA).
The intragranular mineral of expanding material distribute: in the container of silicon system, put into expanding material, pour into epoxy resin and make its sclerosis, utilize ion beam machining machine (SM-09010, NEC system) to carry out section processing to hardening thing, utilize SEM-EDS analytical equipment to confirm.
Tensile strain rate: belong to the tensile strain rate till Books 1 swollen Zhang material モ Le タ Le To I Ru swollen Zhang Try test methods (the swelling property test method of the sand-cement slurry of the attached book 1 of JIS A 6202 based on expanding material) have been measured material age (d) on the 7th according to 6202 pairs of JIS A.
Compressive strength: make the test body of 4 × 4 × 16cm according to JIS R 5201, measured the material age compressive strength of 7 days.
Promote storage test (expanding material): each expanding material 100g is loaded into the square stainless teel pallet of 10 × 10cm and spreads out, under the state of opening on make 20 DEG C of indoor placements 10 of 60%RH.Confirmed the tensile strain rate of sand-cement slurry with the sample reclaiming after 10 days.
Promote storage test (expansive cement): each expansive cement composition is filled in to paper bag and seals, the 35 DEG C of indoor storage of 90%RH January, confirmed the tensile strain rate of sand-cement slurry.
Table 1
As shown in table 1, confirm: under carbon dioxide atmosphere, will contain free lime (f-CaO), hydraulicity compound (hauyne, C 4aF, C 2and dehydrated gyp-(CaSO S) 4) mince heat treated generated the expanding material (experiment No.1-1～1-7) of the embodiment of calcium carbonate of chamotte powder, the tensile strain rate of 2-7d, 5-7d is large, can within 2～7, give cement composition (concrete) with large expansion in material age, the concrete material age compressive strength of 7 days is high, even if the reduction of Long-term Storage, expansion character is also few.
On the other hand, by the expanding material (experiment No.1-8,1-9) of only pulverizing and not carrying out the comparative example of heat treated containing the grog of free lime (f-CaO) under carbon dioxide atmosphere of not moisture hard material, dehydrated gyp-, the tensile strain rate of 2-7d, 5-7d is little, compressive strength is low, and when Long-term Storage, the reduction of expansion character is large.Under carbon dioxide atmosphere by the expanding material of the comparative example of this grog heat treated (experiment No.1-10,1-11), the tensile strain rate of 2-7d is large, but the tensile strain rate of 5-7d is little, compressive strength is low, when Long-term Storage, expansion character reduces slightly, in the time improving adding rate, swell increment is extreme becomes large, and compressive strength changes low.
In addition, do not carry out carbon dioxide treatment and only grog is pulverized to the expanding material (experiment No.1-12,1-13,1-14) of the comparative example obtaining, mixed carbonic acid calcium powder and the expanding material (testing No.1-15) of the comparative example that obtains in not carrying out carbon dioxide treatment and only grog being pulverized to the expanding material obtaining, the tensile strain rate of 2-7d, 5-7d is little, and when Long-term Storage, expansion character reduces.
(experimental example 2)
The composition of grog is fixed as to 50 parts of free limes, 10 parts of hauynes, calcium aluminoferrite (4CaOAl in 100 parts, grog 2o 3fe 2o 3: C 4aF) 5 parts, Calucium Silicate powder (2CaOSiO 2: C 2s) 30 parts of 5 parts, dehydrated gyp-, make flow, treatment temp, the reaction times of carbonic acid gas change according to the mode shown in table 2, in addition, carries out similarly to Example 1.Show the result in table 2.
Table 2
As shown in table 2, confirm: carbon dioxide treatment condition is made as to carbon dioxide flow 0.01～0.1L/min, 200～800 DEG C of temperature and generates in the situation that the manufacture method of the expanding material of the embodiment of calcium carbonate obtains adopting (experiment No.1-4, experiment No.2-1～2-9), the tensile strain rate of 2-7d, 5-7d is large, can within 2～7, give cement composition (concrete) with large expansion in material age, the concrete material age compressive strength of 7 days is high, even if the reduction of Long-term Storage, expansion character is also few.
On the other hand, the temperature of carbon dioxide treatment is made as to 1000 DEG C and in situation that the manufacture method that do not generate the expanding material of the comparative example of calcium carbonate obtains adopting (experiment No.2-10), the tensile strain rate of 2-7d, 5-7d is little, and when Long-term Storage, expansion character reduces.
(experimental example 3)
Process commercially available expanding material, in addition, carried out similarly to Example 1.Show the result in table 3.
Commercially available expanding material A: 50 parts of free limes, 12 parts of hauynes, calcium aluminoferrite (4CaOAl 2o 3fe 2o 3) 5 parts, Calucium Silicate powder (2CaOSiO 2) 30 parts of 3 parts, dehydrated gyp-.
Commercially available expanding material B: 52 parts of free limes, calcium aluminoferrite (4CaOAl 2o 3fe 2o 3) 4 parts, Calucium Silicate powder (2CaOSiO 2) 10 parts, Calucium Silicate powder (3CaOSiO 2) 20 parts of 12 parts, dehydrated gyp-.
Table 3
As shown in table 3, confirm: the commercially available expanding material heat treated forming being minced by the chamotte powder that contains free lime, hydraulicity compound and dehydrated gyp-under carbon dioxide atmosphere the expanding material that has generated the embodiment of calcium carbonate (experiment No.3-1,3-2,3-4,3-5) be not compared with generating the expanding material (testing No.3-3,3-6) of comparative example of calcium carbonate, the tensile strain rate of 2-7d, 5-7d is large, the material age compressive strength of 7 days of cement composition is high, even Long-term Storage, the reduction of expansion character is also few.
(experimental example 4)
Substitute carbonic acid gas with the waste gas of lime firing furnace, processed commercially available expanding material A, in addition, carry out similarly to Example 1.The waste gas of lime firing furnace consists of CO 2: 40%, O 2: 7%, CO:3%, N 2: 50%.Show the result in table 4.
Table 4
As shown in table 4, confirm: the waste gas of use lime firing furnace has carried out the expanding material of carbonating (experiment No.4-1) and carried out the Comparatively speaking expansion character raising of expanding material (experiment No.3-2) of carbonating with using carbonic acid gas.
(experimental example 5)
Carry out the grog of the composition shown in preparation table 5 as raw material with Wingdale, normal portland cement, preparation comprises carbonating process after or the expanding material of 20 parts of 80 parts, the grog of not carbonating processing and dehydrated gyp-s, in 100 parts of cement compositions that comprises cement and expanding material, use 7 parts of expanding materials, similarly carried out with experimental example 1 in addition.Show the result in table 5.
< uses material >
CaO raw material: Wingdale
Cement: normal portland cement, commercially available product
CaSO 4raw material: dehydrated gyp-, Brian specific surface area 3000cm 2/ g
Table 5
As shown in table 5, confirm: to will contain free lime (f-CaO), hydraulicity compound (hauyne, C under carbon dioxide atmosphere 4aF, C 2s, C 3and dehydrated gyp-(CaSO S) 4) mince heat treated generated the expanding material (experiment No.5-1) that has further added the embodiment of dehydrated gyp-in the material of calcium carbonate of chamotte powder, compared with not generating the expanding material (experiment No.5-2) of comparative example of calcium carbonate, the tensile strain rate of 2-7d, 5-7d is large, the material age compressive strength of 7 days of cement composition is high, even Long-term Storage, the reduction of expansion character is also few.
(experimental example 6)
Utilization has used the expansive cement of the expanding material of preparing in experiment No.3-2 to implement outstanding test.20 DEG C indoor, expanding material in 100 parts of expansive cement compositions that is comprising cement and expanding material is that 7 parts, the sand-cement slurry of water/cement composition ratio=50%, cement composition/sand ratio=1/3 carry out mixing, the mixing time after material drops into is changed according to the mode shown in table 6.Be explained, the commercially available expanding material A that uses experiment to use in No.3-3, devotes cement and expanding material respectively according to the mode of carrying out in common fresh concrete equipment in the situation of mixing machine and tests similarly.Show the result in table 6.
< gives prominence to test method >
The sand-cement slurry of mixing mistake is shaped to the tabular of 20 × 20 × 5cm and makes surface for level and smooth, after 20 DEG C of 60% indoor health 6 months, observe having or not that sand-cement slurry surface confirms to give prominence to.
Table 6
As shown in table 6, used and chamotte powder minced to heat treated under carbon dioxide atmosphere and generated the expansive cement (experiment No.6-1, No.6-2) of the expanding material of the embodiment of calcium carbonate, even mixing time shorten do not produce yet outstanding; But will not generate that the expanding material of comparative example of calcium carbonate and cement drop into simultaneously and the material (experiment No.6-3, No.6-4) that obtains, when mixing time shorten produced outstanding.
(experimental example 7)
Use expanding material and the economization agent in experiment No.2-3, prepared to evaluate sand-cement slurry physical property.In 100 parts of expansive cement compositions that comprise cement and expanding material, coordinate 7 parts of expanding materials, 2 parts of economization agents are replaced into the form of water and coordinate with respect to 100 parts of expansive cement compositions.Carry out mixingly the indoor sand-cement slurry by (water+economization agent)/cement composition ratio=50%, cement composition/sand ratio=1/3 of 20 DEG C, investigated expansion characteristics.Also carried out same test for the commercially available expanding material A using in experiment No.3-3 in addition.Show the result in table 7.
(use material)
Economization agent: エ ス ケ mono-ガ mono-De, electrochemical industry system, commercially available product
Table 7
Experiment No. Expanding material Economization agent 0 1d 2d 3d 5d 7d 2-7d 5-7d Appendix
2-3 CO 2Process 0 0 80 300 440 500 550 250 50 Embodiment
7-1 CO 2Process 2 0 70 390 680 810 880 490 70 Embodiment
3-3 Commercially available expanding material A 0 0 200 380 420 450 460 80 10 Comparative example
7-2 Commercially available expanding material A 2 0 190 490 550 580 600 110 20 Comparative example
As shown in table 7, confirm: to chamotte powder being minced to heat treated generated the expanding material (experiment No.7-1) that has further added the embodiment of economization agent in the material of calcium carbonate under carbon dioxide atmosphere, with to not generating compared with the expanding material (experiment No.7-2) that has further added the comparative example of economization agent in the material of calcium carbonate, the tensile strain rate of 2-7d, 5-7d significantly improves.
Utilizability in industry
By expanding material of the present invention and manufacture method thereof, can within 2～7, give concrete with large expansion in material age, initial compressive strength is also high, storage stability also improves and can circulate with expansive cement, even if mixing time shortens and also do not produce outstandingly etc., therefore can be widely used in civil construction field.

Claims (8)

1. an expanding material, is characterized in that, the heat treated that under carbon dioxide atmosphere, the grog that contains free lime, hydraulicity compound and dehydrated gyp-or chamotte powder minced also generates calcium carbonate and obtains,
Wherein, carry out carbonating processing under carbon dioxide atmosphere time, the temperature of container is 200～800 DEG C,
And the content of calcium carbonate is 0.5～10 quality % in described expanding material.
2. expanding material according to claim 1, wherein, contains the particle that has free lime, hydraulicity compound, dehydrated gyp-and calcium carbonate in same particle.
3. expanding material according to claim 1, wherein, Brian specific surface area is 1500～9000cm 2/ g.
4. expanding material according to claim 1, wherein, to described grog or chamotte powder being minced to heat treated generate calcium carbonate and in the material that obtains, further add dehydrated gyp-under carbon dioxide atmosphere.
5. expanding material according to claim 1, wherein, to described grog or chamotte powder being minced to heat treated generate calcium carbonate and in the material that obtains, further add economization agent under carbon dioxide atmosphere.
6. a cement composition wherein, coordinates the expanding material described in wantonly 1 in claim 1～5 in cement.
7. according to the manufacture method of the expanding material described in claim 1～5 wantonly 1, it is characterized in that, the heat treated that under carbon dioxide atmosphere, the grog that contains free lime, hydraulicity compound and dehydrated gyp-or chamotte powder minced, generates calcium carbonate.
8. the manufacture method of expanding material according to claim 7, wherein, in carbonating processing vessel, filling grog or chamotte powder minces, is that temperature in 0.01～0.1L/min, container is to generate calcium carbonate under the condition of 200～800 DEG C at the carbon dioxide flow of every 1L volume of described container.
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